CN1386490A

CN1386490A - Composition based on silicone oil structurized in hardened form, especially use in beauty cosmetics

Info

Publication number: CN1386490A
Application number: CN02123279A
Authority: CN
Inventors: F·托尔尼尔哈克
Original assignee: LOreal SA
Current assignee: LOreal SA
Priority date: 2001-06-14
Filing date: 2002-06-14
Publication date: 2002-12-25
Also published as: DE60220119D1; EP1266647B1; FR2825915A1; EP1815840A1; JP2002370919A; DE60220119T2; EP1266647A1; FR2825915B1; US20030072730A1; ATE362356T1; ES2287228T3

Abstract

A physiologically acceptable composition, especially a cosmetic composition, comprising a liquid fatty phase comprising at least one silicone oil, structured with a polymer with a weight-average molecular mass ranging from 500 to 500 000, comprising at least one moiety comprising: at least one polyorganosiloxane group comprising from 1 to 1 000 organosiloxane units in the chain of the moiety of in the form of a graft, and at least two groups capable of establishing hydrogen interactions, the polymer being solid at room temperature and soluble in the liquid fatty phase at a temperature of from 25 to 250 DEG C., and the liquid fatty phase comprising partially or totally volatile oil(s) with a flash point greater than or equal to 40 DEG C. and greater than the softening point of the polymer, on condition that the composition comprises at least 10% by mass of a non-volatile oil and/or of a pasty or viscous product.

Description

Composition based on silicone oil structured in hardened form, in particular for use in cosmetic preparations

Technical Field

The present invention relates to a care and/or treatment and/or make-up composition for the skin, including the scalp and/or the human lips, comprising a liquid fatty phase comprising at least one silicone oil gelled with a specific polymer, in particular in the form of an injection-moulded cosmetic product, in particular in the form of a cosmetic strip, for example a lipstick, the application of which produces a shiny and migration-resistant attachment.

The invention relates more particularly to cosmetic and dermatological compositions, such as cosmetic preparations, which have a retention capacity, transfer resistance and stability.

Prior Art

Structured, i.e. gelled and/or hardened, liquid fatty phases are often found in cosmetic or dermatological preparations; this is especially the case in solid compositions such as deodorants, lipsticks, eye shadows, masking products and casting powders. This structuring is obtained with the aid of waxes or fillers. Unfortunately, these waxes and fillers have a tendency to make the composition matte, which is not always desirable, particularly for use in lipsticks.

For the purposes of the present invention, the expression "liquid fatty phase" means a fatty phase which is liquid at room temperature (25 ℃) and atmospheric pressure (760mmHg) and which consists of one or more fatty substances which are liquid at room temperature, also known as oils, which are mutually compatible and contain silicone oils.

For the purposes of the present invention, the expression "structured liquid fatty phase" means that this structured phase does not flow between the fingers and is at least thickened.

In addition to limiting migration of the phase into wrinkles and fine lines after attachment to the skin or lips, which is particularly desirable for lipstick or eye shadow, the structuring of the liquid fatty phase makes it possible to limit in particular its exudation from the solid composition. In particular, the high migration of the liquid fatty phase carrying the dye leads to an unsightly effect around the lips or eyes, which accentuates wrinkles and fine lines in particular. This migration is often mentioned by women as a major drawback of traditional lipsticks and eye shadows. The term "migration" means that the composition attached to the lips or skin moves beyond its original application line.

Gloss is essentially related to the properties of the liquid fatty phase. Thus, in order to improve the gloss of a lipstick, the content of waxes and fillers in the composition may be reduced, but in this case the migration of the liquid fatty phase is increased. In other words, the amount of wax and filler required to produce a bar of appropriate hardness is a limiting factor in the gloss of the deposit.

Document EP-A-1068856[1] describes wax-free solid cosmetic compositions comprising ｃA liquid fatty phase structured with ｃA polymer, in which the fatty phase is predominantly non-silicone oil.

The use of fatty phases based on silicone oils currently makes it possible to obtain cosmetic compositions with long-lasting retention, i.e. in particular good retention of the colour over time (no colour change and no discolouration), when these oils are non-volatile or relatively non-volatile, and transfer-resistant compositions, i.e. compositions which do not adhere to a support such as a glass, cup, fabric or cigarette which is in contact with the cosmetic film, when the silicone oils are volatile.

At present, the use of silicone oils in cosmetics is limited by the small number of molecules that enable these media to gel and thus enable the production of compositions in solid form, such as pour-on lipsticks or foundations. The use of cosmetic compositions whose fatty phase is mainly based on silicones, in most cases creates problems of compatibility with the ingredients traditionally used in cosmetics.

In the documents US-A-5874069[2], US-A-5919441[3], US-A-6051216[4], WO-A-02/17870[8] and WO-A-02/17871[9], cosmetic compositions are prepared, such as deodorant gels or sticks, comprising A silicone oil phase gelled with A wax based on polysiloxanes and polyamides or with A polymer containing siloxane groups and groups capable of interacting with hydrogen.

For use as a deodorant, the problems of migration of the oily phase into wrinkles and fine lines and retention and transfer resistance of the composition as in the case of the above-mentioned cosmetic preparations do not arise.

Disclosure of Invention

An object of the present invention is in particular a care and/or make-up and/or treatment composition for the skin and/or the lips, intended to overcome these drawbacks.

Surprisingly, the applicant has found that it is possible to structure, in the form of a cosmetic or care preparation, a liquid fatty phase based on silicone oils comprising a volatile oil with a suitable flash point, using specific polymers, without or in the presence of a small amount of wax, the application of which produces a glossy or matt and migration-resistant film and enhances the retention and/or transfer resistance of these products.

The invention applies not only to cosmetic preparations for the lips, such as lipsticks, lip pencils and lip transparencies, but also to care and/or treatment preparations for the skin, including for the scalp and for the lips, such as sunscreen sticks for the skin, the face or the lips, or lipsticks; cosmetic preparations for application to the skin, including human faces and the human body, such as foundations in the form of a stick or a dish, concealer preparations and temporary tattoo preparations; application to hygiene and cleaning articles, in particular in the form of strips; and to make-up products for the eyes, such as eyeliners, in particular penlike and mascara, especially cakes for keratin fibres (eyelashes, eyebrows or hair).

More specifically, an object of the present invention is a liquid fatty phase comprising at least one silicone oil, structured with at least one gelling agent consisting of a polymer (homopolymer or copolymer) having a weight-average molecular weight of 500-500000, comprising at least one fraction comprising:

at least one polyorganosiloxane group, consisting of a polyorganosiloxane in the chain of the moiety or in the form of a graft

From 1 to 1000 organosiloxane units of the formula, and

-at least two groups capable of establishing an interaction with hydrogen, selected from esters, amides, sulfonamides,

Carbamate, thiocarbamate, urea, thiourea, oxamido, guanidino,

And biguanide groups, and combinations thereof, with the proviso that at least one group is not an ester group,

the polymer is solid at room temperature and soluble in the liquid fatty phase at 25-250 ℃,

the liquid fatty phase is partially or totally composed of a volatile oil having a flash point greater than or equal to 40 ℃ and higher than the softening point of the gelling polymer, and forms a physiologically acceptable medium with the polymer.

The flash point is the temperature at which the fuel ignites when it comes into contact with the flame.

Advantageously, the flash point of the volatile oil is greater than 60 ℃, preferably greater than 80 ℃, more preferably greater than 93 ℃.

It is also preferred that the flash point of the volatile oil is less than or equal to 160 deg.C, more preferably less than or equal to 135 deg.C.

The term "volatile oil" refers to any non-aqueous medium that evaporates in less than 1 hour upon contact with the skin at room temperature and atmospheric pressure. Volatile cosmetic oil(s) which are liquid at room temperature, in particular having a vapour pressure of 10 measured at room temperature and atmospheric pressure^-3-300mmHg (0.266Pa-40000Pa), preferably 0.02mmHg-300mmHg (2.66Pa-40000Pa), more preferably 0.1-90mmHg (13Pa-12000 Pa).

According to the invention, the volatile oil may be a silicone oil or a non-silicone oil.

Thus, the invention can be carried out with the following different fatty phases:

1) from a mixture of oils comprising at least one non-volatile silicone oil and at least one volatile silicone oil

A fat phase of composition;

2) from an oil comprising at least one non-volatile silicone oil and at least one non-silicone volatile oil

A fatty phase consisting of the mixture of (a);

3) comprises at least one non-volatile silicone oil, at least one volatile silicone oil and at least one

A fatty phase consisting of a mixture of oils of volatile non-silicone oils;

4) comprising at least one volatile silicone oil, one non-volatile non-silicone oil and optionally at least one

A fatty phase consisting of a mixture of oils of at least one volatile non-silicone oil; and

5) a fatty phase consisting only of some volatile silicone oils.

In cases 1), 2) and 3), the mixture may also comprise a non-volatile non-silicone oil.

Generally, the volatile oil is present in an amount of from 3% to 89.4% by weight of the total composition, preferably from 5% to 75% by weight of the total composition, more preferably from 10% to 60%, for example from 20% to 50%.

According to the invention, the volatile silicone oil may be chosen from linear or cyclic silicone oils having a flash point of at least 40 ℃, such as linear or cyclic polydimethylsiloxanes, polymethylphenylsiloxanes, dimethicone copolyols, alkylmethicone copolyols, hexadecyldimethicone, silicones containing alkylglyceryl ether groups, silicones containing pendant amino groups and dilauroyl triacyl trimethacrylsiloxane siloxysilicate.

Examples of such volatile oils that may be mentioned include the compounds given in table 1 below.

TABLE 1

Compound (I)	Flash point (℃)	Viscosity of the oil (cSt)
Compound (I)	Flash point (℃)	Viscosity of the oil (cSt)	Octyl trimethicone Hexyltrimethicone Decamethylcyclopentasiloxane (Cyclopentasiloxane or D5) Octamethylcyclotetrasiloxane (Cyclotetradimethylsiloxane or D4) Decamethylcyclohexasiloxane (D6) Decamethyltetra (methyl tetra)Siloxane (L4) KF 96A from Shin Etsu PDMS (polydimethylsiloxane) DC 200 from Dow Corning (1.5 cSt) PDMS DC 200(2 cSt) from Dow Corning PDMS DC 200(5 cSt) from Dow Corning PDMS DC 200(3 cSt) from Dow Corning	93 79 72 55 93 63 94 56 87 134 102	1.2 1.2 4.2 2.5 7 1.7 6 1.5 2 5cSt 3cSt

According to the invention, the volatile non-silicone oil may be chosen from hydrocarbon-based oils and volatile esters and ethers, such as volatile hydrocarbons, for example isododecane and isohexadecane, C₈-C₁₆Isoparaffins, isohexyl or isodecyl neopentanoate, and mixtures thereof.

As examples of volatile non-silicone oils that can be used in the present invention, the compounds in table 2 below can be mentioned.

TABLE 2

Compound (I)	Flash point (℃)
Compound (I)	Flash point (℃)	Isododecane Isohexadecane Isodecyl neopentanoate Propylene glycol n-butyl ether 3-Ethoxypropionic acid ethyl ester Propylene glycol methyl ether acetate Isopar L(C₁₁-C₁₃Isoparaffin) Isopar H(C₁₁-C₁₂Isoparaffin)	43 102 118 60 58 46 62 56

According to the invention, these volatile oils facilitate in particular the application of the composition to the skin, the lips or the integuments. These oils may be hydrocarbon-based oils, silicone oils optionally containing pendent or at the end of the silicone chain alkyl or alkoxy groups, or mixtures of these oils.

As volatile oils which can be used in the present invention, mention may be made of linear or cyclic silicone oils having a viscosity at room temperature of less than or equal to 8cSt and containing in particular from 2 to 7 silicon atoms, these silicones optionally comprising alkyl or alkoxy groups containing from 1 to 10 carbon atoms. As volatile silicone oils which can be used in the present invention, mention may in particular be made of octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, heptamethyloctyltrisiloxane, hexamethyldisiloxane, decamethyltetrasiloxane and dodecamethylpentasiloxane, and mixtures thereof. A volatile oil which can also be used is the commercial KF 96A at 6 cSt from Shin Etsu, which has a flash point of 94 ℃.

As further volatile oils which can be used in the present invention, mention may be made of hydrocarbon-based volatile oils containing from 8 to 16 carbon atoms and their mixtures, in particular branched C₈-C₁₆Alkanes, e.g. C₈-C₁₆Isoparaffins (also known as isoparaffins), isododecane, isodecane, isohexadecane and oils such as those sold under the trade names Isopars or permethyls, and branched chainsC of (A)₈-C₁₆Esters, such as isohexyl pivalate, and mixtures thereof.

Advantageously, the composition contains at least one volatile silicone oil having a flash point greater than 40 ℃.

The liquid fatty phase advantageously contains at least 40%, preferably at least 50% by weight of silicone oil, advantageously having a viscosity of less than 5000cSt, more preferably less than 3000cSt, since the silicone polymer used in the present invention is more readily soluble in low viscosity silicone oils. It may also contain other non-silicone oils or mixtures of oils.

The silicone oils which can be used in the present invention may be in particular volatile or non-volatile, linear or cyclic Polydimethylsiloxanes (PDMSs) which are liquid at room temperature; polydimethylsiloxanes comprising alkyl, alkoxy or phenyl groups, these groups being pendent and/or at the end of a siloxane chain, each group containing from 2 to 24 carbon atoms; phenylsiloxanes such as phenyltrimethicone, phenyldimethicone, phenyltrimethylsiloxydiphenylsiloxane, diphenyldimethicone, diphenylmethyldiphenyltrisiloxane and 2-phenylethyltrimethylsiloxysilicate.

The liquid fatty phase may also contain other oils other than silicone oils, for example polar oils such as:

hydrocarbon-based plants with a high content of triglycerides consisting of fatty acid esters of glycerol

Vegetable oils in which the chain lengths of the fatty acids may vary, these chains possibly being straight or branched

Chained, saturated or unsaturated; these oils are especially wheat germ oil, corn oil and sunflower oil

Seed oil, kokum oil, castor oil, sweet almond oil, macadamia nut oil, almond oil,

Soybean oil, rapeseed oil, cottonseed oil, alfalfa oil, poppy oil, pumpkin oil, sesame oil,

Bone marrow oil, fructus Pyri oil, hazelnut oil, grape seed oil, black currant seed oil, evening primrose oil,

Millet oil, barley oil, quinoa oil, olive oil, rye oil, safflower oil, and Chinese gooseberry

Oil, passion flower oil or musk rose oil; or triglycerides of caprylic acid or capric acid,

such as those sold by the company Stearines Bubois or by the company Dynamit Nobel

Those sold by companies under the names Miglyol 810, 812 and 818;

-formula R₅COOR₆Wherein R is₅It is shown to contain 1 to 40 of,

preferred are straight-chain or branched higher fatty acid residues of 7 to 19 carbon atoms, R₆

Denotes branched hydrocarbons containing 1 to 40, preferably 3 to 20, carbon atoms

And R is₅+R₆≧ 10, such as Purcellin oil (cetostearyl alcohol)

Octanoate esters of (cetostearyl), isononyl isononanoate, benzoic acid C₁₂-C₁₅

Of alkyl esters, isopropyl myristate, 2-ethylhexyl palmitate, or of alcohols or polyols

Caprylate, caprate or ricinoleate; hydroxylated esters, e.g. isostearic acid

An acyl ester or diisostearyl malate; and esters of pentaerythritol;

-synthetic esters containing 10 to 40 carbon atoms;

-C₆-C₂₆fatty alcohols, such as oleyl alcohol; and

mixtures thereof.

The liquid fatty phase may also comprise apolar oils such as linear or branched hydrocarbons or fluorocarbons of synthetic or mineral origin, which may be volatile or non-volatile, for example volatile liquid paraffins (such as isoparaffins or isododecanes) or non-volatile liquid paraffins and derivatives thereof, petroleum petrolatum, polydecenes, hydrogenated polyisobutenes such as parleam and squalane, and mixtures thereof.

Generally, the liquid fatty phase represents from 5% to 99%, preferably from 20% to 75% by weight of the total composition.

According to the invention, the composition also comprises a dye. The dye may be insoluble in the medium, for example may consist of a pigment or nacres, or the dye may be soluble in oil, for example may consist of a liposoluble dye.

According to the invention, the composition generally also comprises solid particles selected from fillers and pigments and mixtures thereof. Generally, the average size of the solid particles is from 10 nm to 50 microns, preferably from 50 nm to 30 microns, more preferably from 100 nm to 10 microns.

Fillers used in cosmetic compositions generally have the purpose of absorbing perspiration and sebum or of providing a matte effect. According to the invention, they also make it possible to structure the liquid fatty phase comprising the silicone oil and to enhance the retention and/or transfer resistance, as well as the thermal stability of the composition.

In anhydrous compositions in stick form, such as lipstick and masking products in tube form, these fillers also make it possible, even when heated (45-47 ℃), to limit the exudation of the oil from the tube and/or to limit the migration of the liquid fatty phase outside its original application line, in particular into wrinkles and fine lines.

The term "pigment" refers to any solid particle that is insoluble in the composition and is used to give and/or modify color and/or sparkle appearance.

These pigments can provide both a sweat and sebum absorbing effect and an effect of coloring or modifying the appearance of the composition (i.e., a cosmetic, therapeutic or body hygiene article). In the present invention, they also participate in structuring the liquid fatty phase.

These fillers or pigments may be hydrophobic or hydrophilic. When these fillers or pigments are hydrophilic particles, their dispersion in the composition can be promoted by coating them with a film of hydrophobic compound or by adding amphiphilic silicones to the composition, or by adding dispersants or by grafting hydrophobic compounds.

The hydrophobic pigments or fillers may also consist of more or less spherical particles of crosslinked hydrophobic polymers or copolymers. Examples of crosslinked hydrophobic polymers and copolymers that may be mentioned include:

1 deg. fluoropolymers, such as polytetrafluoroethylene powder and tetrafluoroethylene with olefins (e.g. ethylene)

Or propylene) copolymer powder;

2 ℃) siloxane elastomers, e.g. polymethylsilsesquioxane

(polyemthylsilsoquioxane) powder;

3 °) polyolefin, such as polyethylene;

4 °) polyalkylmethacrylate, such as polymethyl methacrylate;

5 °) polyamide;

6 °) polystyrene and derivatives thereof;

7 °) polyester;

8 °) polyacrylic acid; and

9 ℃) polyurethanes, for example 1, 6-Hexamethylene Diisocyanate (HDI)/trimethylol caprolactone powder.

Of course, instead of spherical particles, it is also possible to use fibers having hydrophobic properties, in particular fibers of the polymers and copolymers mentioned above, and fillers in platelet form.

The solid particles may also consist of pigments and/or nacres for obtaining a covering cosmetic effect, i.e. a cosmetic effect that does not reveal the skin, the lips or the covering. These particles also make it possible to reduce the sticky feel of the composition.

The pigments may be white or colored, inorganic and/or organic, coated or uncoated. Inorganic pigments which may be mentioned are titanium dioxide, optionally surface-treated, zirconium oxide or cerium oxide, and also iron oxide, chromium oxide, manganese violet, ultramarine blue, chromium hydroxide and ferric blue. Organic pigments which may be mentioned are carbon black, pigments of the D & C type, lake pigments based on carmine or on barium, strontium, calcium or aluminum. The pigment may comprise from 0% to 40%, preferably from 1% to 35%, more preferably from 2% to 25% by weight of the total composition.

The pearlescent pigment (or nacre) may be selected from white pearlescent pigments such as titanium or bismuth oxychloride coated mica; colored pearlescent pigments such as titanium mica containing iron oxide, in particular titanium mica with ferric blue or chromium oxide, titanium mica with organic pigments of the abovementioned type, and pearlescent pigments based on bismuth oxychloride. They may represent from 0% to 20%, preferably from 0.1% to 15% by weight of the total composition.

When the pigments or fillers are hydrophilic, they may be coated with a film of hydrophobic compound in order to introduce them into the liquid fatty phase of the composition of the invention, or they may be subjected to a hydrophobic treatment.

The coating may consist of a surface treatment of the particles prior to their introduction into the fat phase, for example during their manufacture or in situ.

The coating or surface treatment may be a fluorine-containing coating such as a perfluoroalkyl mono-or diester of phosphoric acid (acid or salt), perfluoropolyether, a perfluorocarboxylic acid or perfluorosulphonic acid, or a perfluoroalkyl diethanolamine phosphate.

The coating may be a fluorosilicone based coating or graft, for example, with a perfluoroalkyl containing silane.

The surface treatment can also be carried out using siloxane derivatives, for example grafting with reactive siloxanes initially containing hydrosilane (hydrosilane) groups, grafting with diorganosilanes such as dimethylchlorosilane or with alkylalkoxysilanes, grafting with silanes containing glycidoxypropyl groups, coating with polyglycerolated siloxanes, or coating with siloxane-grafted acrylic copolymers or siloxane-g-polyacrylic acids.

Coatings with N-acyl amino acids such as N-lauroyl lysine, fatty acids or fatty acid salts of the stearic acid type, lecithin and ester oils may also be used.

Generally, the composition comprises from 0.1% to 90%, preferably from 1% to 70%, more preferably from 2% to 50%, for example from 5% to 25%, of solid particles relative to the total weight of the composition.

It is also possible to use at least one amphiphilic silicone as surfactant between the hydrophilic particles and the hydrophobic silicone phase to facilitate the dispersion of the hydrophilic particles.

These amphiphilic silicones comprise a silicone moiety compatible with the silicone-based medium of the composition of the invention and a hydrophilic moiety, for example the hydrophilic moiety may be the residue of a compound selected from an alcohol or polyol containing from 1 to 12 hydroxyl groups; a residue of a polyoxyalkylene compound containing at least two oxyalkylene moieties and containing from 0 to 20 oxypropylene moieties and/or from 0 to 20 oxyethylene moieties. Such hydrophilic moieties thus have an affinity for the hydrophilic particles and facilitate their dispersion in the silicone medium.

The amphiphilic silicone may be an oil without gelling activity, such oil may consist of:

-dimethicone copolyol (copolyol), optionally comprising phenyl groups,

-an alkyl-polysiloxane copolyol,

polyglycerolated silicones, i.e. silicones containing alkyl glyceryl ether groups,

-a silicone comprising perfluorinated side groups and glycerinated side groups,

-a silicone comprising pendant polyoxyethylene/polyoxypropylene groups and pendant perfluorinated groups,

copolymers containing siloxane blocks and hydrophilic blocks other than polyethers, e.g. polyoxoans

Oxazoline or polyethyleneimine.

-a graft copolymer of the polysaccharide type grafted with silicones,

copolymerization containing siloxane blocks and poly (ethylene oxide/propylene oxide) blocks

A compound (I) is provided.

The amphiphilic silicone used in the present invention may also be at least one partially crosslinked hydrophilic resin.

Examples of such resins that may be mentioned include:

crosslinked silicone resins containing alkyl-polyether groups, such as polyethylene oxide (PEO) and

polyethylene oxide/polypropylene oxide (PEO/PPO), as described in US-A-5412004[6]

Above, and

siloxane resins partially crosslinked with α, omega-dienes and containing hydrophilic components

PEO/PPO side chains and hydrophobic alkyl side chains, as in EP-A-1048686[7]

Those described above. Obtained by reaction with PEO/PPO having only one vinyl terminus

To obtain the hydrophilic side chain, the alkyl side is formed by reaction with an aliphatic chain α -olefin

And (3) a chain.

The total amount of amphiphilic silicone may range from 0.1% to 20%, preferably from 0.1% to 10% by weight of the total composition.

In the amphiphilic silicone resin, the silicone moiety is advantageously formed from polydimethylsiloxane.

In the compositions of the invention, the polymer used as gelling agent is generally used in an amount of from 0.5% to 80%, preferably from 2% to 60%, more preferably from 5% to 40%, by weight of the total composition.

Further, the mass ratio of the gelling agent polymer/silicone oil is preferably 0.1% to 50%.

The polymers used as gelling agents in the compositions according to the invention are polymers of the polyorganosiloxane type, such as those described in documents U.S. Pat. No. 2, 5874069,2, U.S. Pat. No. 3, 5919441,3, U.S. Pat. No. 3, 6051216,4 and U.S. Pat. No. 5981680,5.

According to the invention, the polymers used as gelling agents belong to the following two families:

1) polyorganosiloxanes comprising at least two groups capable of establishing an interaction with hydrogen, this

Two groups are located in the polymer chain; and/or

2) Polyorganosiloxanes comprising at least two groups capable of establishing an interaction with hydrogen, this

Two groups are located in the graft or branch.

Use of the polymers according to the invention is a solid pre-dissolved in a solvent having an interaction with hydrogen, such as C, capable of breaking the hydrogen interaction of the polymer, before being placed in the silicone oil according to the invention₂-C₈Lower alcohols, in particular ethanol, n-propanol or isopropanol. These hydrogen-interacting "destructive" solvents may also be used as co-solvents. These solvents are then stored in the composition or expelled by selective evaporation, as is well known to those skilled in the art.

The polymer comprising two groups capable of establishing hydrogen interactions in the polymer chain may be a polymer comprising at least oneA polymer having moieties corresponding to the formula:

wherein:

1)R¹、R²、R³and R⁴Which may be the same or different, represent a group selected from:

-linear, branched or cyclic, saturated or unsaturated C₁-C₄₀Based on hydrocarbons

A group, possibly containing in its chain one or more oxygen, sulfur and/or nitrogen atoms, and

and may be partially or fully substituted with fluorine atoms,

-C₆-C₁₀aryl, optionally with one or more C₁-C₄The substitution of the alkyl group is carried out,

polyorganosiloxane chains possibly containing one or more oxygen, sulphur and/or nitrogen atoms;

2) the groups X, which may be identical or different, represent a linear or branched C₁-C₃₀Alkylene oxide

An alkyldiyl group, which may contain one or more oxygens and/or/and

or a nitrogen atom;

3) y is saturated or unsaturated C₁-C₅₀Straight or branched chain divalent alkylene, alkylidene

Aryl, cycloalkylene, alkylarylene or arylalkylene radicals, possibly containing one or more

A plurality of oxygen, sulfur and/or nitrogen atoms, and/or with one of the following atoms or groups of atoms

Is a substituent group:

fluorine, hydroxy, C₃-C₈Cycloalkyl radical, C₁-C₄₀Alkyl radical, C₅-C₁₀Aryl, heteroaryl, and heteroaryl,

Optionally 1-3C₁-C₃Alkyl-substituted phenyl, C₁-C₃Hydroxyalkyl and

C₁-C₆aminoalkyl, or

4) Y represents a group corresponding to the formula:

wherein:

-T represents a linear or branched, saturated or unsaturated C₃-C₂₄Trivalent or tetravalent based on

The hydrocarbon radical, optionally substituted with a polyorganosiloxane chain, and possibly containing one or more

A plurality of atoms selected from O, N and S, or T represents a trivalent atom selected from N, P and Al

Atom, and

-R⁵represents a straight or branched chain C₁-C₅₀Alkyl or polyorganosiloxane chains, possibly containing

With one or more esters, amides, urethanes, thiocarbamates, ureas, thioureas, and-

Or sulfonamide groups, possibly attached to another chain of the polymer;

5) the groups G, which may be identical or different, represent divalent groups selected from:

wherein R is⁶Represents a hydrogen atom or a straight or branched C₁-C₂₀Alkyl, with the proviso that at least 50% of the radicals R of the polymer are⁶Represents a hydrogen atom and at least two of the groups G of the polymer are groups other than:

6) n is an integer from 2 to 500, preferably from 2 to 200, and m is an integer from 1 to 1000, preferably from 1 to 700, more preferably from 6 to 200.

According to the invention, the radical R of the polymer¹、R²、R³And R⁴Is preferably selected from methyl, ethyl, phenyl and 3, 3, 3-trifluoropropyl.

According to the invention, Y may represent various divalent groups, optionally additionally comprising one or two free valencies to establish a bond with other parts of the polymer or copolymer. Preferably Y represents a group selected from:

a) straight chain C₁-C₂₀Preferably C₁-C₁₀The alkylene group of (a) is,

b)C₃₀-C₅₆branched alkylene groups, which may contain cyclic and nonconjugated unsaturation,

c)C₅-C₆a cyclic alkylene group,

d) optionally one or more C₁-C₄₀An alkyl-substituted phenylene group, a phenylene group substituted with an alkyl group,

e) c comprising 1-5 amide groups₁-C₂₀An alkylene group or a substituted alkylene group,

f) containing one or more groups selected from hydroxy, C₃-C₈Cycloalkanes, C₁-C₃Hydroxyalkyl and C₁-C₆C of substituents of alkylamino groups₁-C₂₀An alkylene group or a substituted alkylene group,

g) polyorganosiloxane chains having the formula:

wherein R is¹、R²、R³、R⁴T and m are as defined above, and

h) polyorganosiloxane chains having the formula:

the group II polyorganosiloxane may be a polymer comprising at least one moiety corresponding to formula (II):

wherein:

-R¹and R³May be the same or different and is as defined above for formula (I)

In the above-mentioned manner,

-R⁷is represented by the above pair R¹And R³A group as defined, or represents a compound having the formula-X-G-R⁹

Wherein X and G are as defined above for formula (I) and R⁹Represents hydrogen

Atom or straight or branched chain or cyclic, saturated or unsaturated C₁-C₅₀Based on hydrocarbons

Optionally containing in its chain one or more atoms selected from O, S and N,

optionally substituted with one or more fluorine atoms and/or one or more hydroxyl groups; or optionally

With one or more C₁-C₄A phenyl group substituted with an alkyl group,

-R⁸is represented by the formula-X-G-R⁹Wherein, X, G and R⁹As is defined above, the above-mentioned,

-m₁is an integer of 1 to 998, and

-m₂is an integer from 2 to 500.

The polymer used as gelling agent according to the invention may be a homopolymer, i.e. a polymer comprising several identical moieties, in particular moieties of formula (I) or formula (II).

According to the invention, it is also possible to use polymers consisting of copolymers comprising several different moieties of formula (I), i.e. where the group R¹、R²、R³、R⁴X, G, Y, m and nAt least one polymer that differs in one of the moieties. The copolymer may also be formed from moieties of formula (II) wherein the group R¹、R³、R⁷、R⁸、m₁And m₂Is different in at least one of the portions.

Copolymers comprising at least one moiety of formula (I) and at least one moiety of formula (II), which may be the same or different from each other, may also be used.

According to a variant of the invention, it is also possible to use copolymers further comprising at least one hydrocarbon-based moiety comprising two groups capable of establishing hydrogen interactions, chosen from ester, amide, sulfonamide, carbamate, thiocarbamate, urea and thiourea groups, and combinations thereof.

These copolymers may be block copolymers or graft copolymers.

According to a first embodiment of the invention, the groups capable of establishing hydrogen interconnections are amide groups having the formulae-C (O) NH-and-HN-C (O) -.

In this case, the gelling agent may be a polymer comprising at least one moiety having formula (III) or (IV):

orWherein R is¹、R²、R³、R⁴X, Y, m and n are as defined above.

Such a portion may be obtained in the following manner:

or by condensation between α, omega-carboxylic acid terminated siloxanes and one or more diamines according to the following reaction sequence:

or by two molecules of α -unsaturated carboxylic acid with diamine according to the following reaction procedure

The reaction of (a) to obtain:

then, the siloxane was added to the ethylenic unsaturation according to the following procedure:

CH₂＝CH-X¹-CO-NH-Y-NH-CO-X¹-CH＝CH₂

wherein, X¹-(CH₂)₂Corresponding to X as defined above, and Y, R¹、R²、R³、R⁴And m is as defined above;

or by containing α, omega-NH according to the following reaction sequence₂Terminal siloxanes and molecules

Reaction of a diacid of formula HOOC-Y-COOH:

in these polyamides of the formula (III) or (IV), m is preferably from 1 to 700, preferably from 15 to 500, more preferably from 15 to 45, n is in particular from 1 to 500, preferably from 1 to 100, more preferably from 4 to 25,

x is preferably a radical having from 1 to 30 carbon atoms, in particular from 3 to 10 carbon atoms

A straight-chain or branched alkylene chain,

y is preferably a linear or branched or optionally cyclic and/or unsaturated sulfine

Alkyl chains containing from 1 to 40 carbon atoms, especially from 1 to 20 carbon atoms,

preference is given to 2 to 6 carbon atoms, in particular 6 carbon atoms.

In formulae (III) and (IV), the alkylene group representing X or Y may optionally contain in its alkylene portion at least one of the following components:

1 °)1 to 5 amide, urea or urethane groups,

2°)C₅-C₆cycloalkyl radicals, and

3 ℃) optionally with 1 to 3 identical or different C₁-C₃Alkyl-substituted phenylene radicals.

In the formulae (III) and (IV), the alkylene group may also be substituted with at least one member selected from the group consisting of:

-a hydroxyl group,

-C₃-C₈a cycloalkyl group,

1-3 of C₁-C₄₀An alkyl group, a carboxyl group,

optionally 1-3C₁-C₃A phenyl group substituted with an alkyl group,

-C₁-C₃hydroxyalkyl radicals, and

-C₁-C₆an aminoalkyl group.

In these formulae (III) and (IV), Y may also represent:wherein R is⁵Represents a polyorganosiloxane chain and T represents a group having the formula:

wherein a, b and c are each independently an integer of 1 to 10, R¹⁰Is a hydrogen atomOr a group, e.g. R¹、R²、R³And R⁴Those groups as defined.

In the formulae (III) and (IV), R¹、R²、R³And R⁴Preferably each independently represents a straight or branched chain C₁-C₄₀Alkyl, preferably CH₃、C₂H₅、C₃H₇Or an isopropyl group; polyorganosiloxane chains or phenyl groups optionally substituted with 1-3 methyl or ethyl groups.

As previously mentioned, the polymer may comprise the same or different moieties having formula (III) or (IV).

Thus, the polymer may be a polyamide containing moieties of formula (III) or (IV) of different lengths, i.e. a polyamide corresponding to the formula:wherein, X, Y, n and R¹-R⁴Having the meaning given above, m₁And m₂Are different and are chosen within the range of 1 to 1000, p being an integer from 2 to 300.

In this formula, the moieties may be configured to form a block copolymer or a random copolymer or an alternating copolymer. In the copolymer, the moieties may not only have different lengths, but also different chemical structures, e.g. containing different groups Y. In this caseThe copolymer may correspond to the formula:wherein R is¹-R⁴、X、Y、m₁、m₂N and p have the meanings given above and Y¹Different from Y but selected from the group defined for Y. As previously described, the various moieties can be configured to form block copolymers or random copolymers or alternating copolymers.

In this first embodiment of the invention, the gelling agent may also consist of a graft copolymer. Thus, polyamides containing siloxane units can also be grafted or optionally crosslinked with siloxane chains containing amide groups. Such polymers can be synthesized with trifunctional amines.

In this case, the copolymer may contain at least one moiety having the formula:wherein, X¹And X²May be the same or different and has the meaning given for X in formula (I), n is as defined in formula (I), Y and T are as defined in formula (I), R¹¹-R¹⁸Is selected from the group consisting of¹-R⁴Same group, m₁And m₂Is a number from 1 to 1000 and p is an integer from 2 to 500.

In formula (VII), preferred are:

p is 1 to 25, preferably 1 to 7,

-R¹¹-R¹⁸is a methyl group, and the compound is,

-T corresponds to one of the following formulae:

wherein R is¹⁹Is a hydrogen atom or is selected from the group consisting of p-R¹-R⁴A group as defined, R²⁰、R²¹And R²²Each independently a linear or branched alkylene group, more preferably corresponding to the formula:

R²⁰、R²¹and R²²In particular represents-CH₂-CH₂-，

-m₁And m₂In the range of 15 to 500, preferably 15 to 45,

-X¹and X²Is represented by- (CH)₂)₁₀-，

-Y represents-CH₂-。

These polyamides containing grafted siloxane moieties of formula (VII) can be copolymerized with polyamide-siloxanes of formula (II) to form block, alternating or random copolymers. The weight percentage of grafted silicone moieties (VII) in the copolymer is between 0.5 and 30% by weight.

According to the invention, the siloxane units may be in the backbone or skeleton of the polymer, as previously described, but they may also be present in grafted or pendant chains. In the backbone, the siloxane units may be in the form of segments as described above. In the pendant or grafted chains, the siloxane units may occur individually or in segments.

Preferred silicone-based polyamides according to the invention are:

-polyamides of formula (III) wherein m is 15 to 50;

mixtures of two or more polyamides, at least one of the polyamides having a value of m

15 to 50 and at least one polyamide having an m value of 30 to 50;

-a polymer of formula (V), m₁Selected in the range of 15-50, m₂In the range of 30-500

Select within the enclosure, and correspond to m₁In a proportion of 1 to 99% by weight, based on the total weight of the polyamide

And m₂Corresponding proportions of 1 to 99% by weight, based on the total weight of the polyamide;

-a mixture of polyamides of formula (III) combining the following components:

1)80 to 99% by weight of a polyimide in which n is 2 to 10, in particular 3 to 6

An amine, and

2)1 to 20% by weight of a compound in which n is in the range from 5 to 500, in particular from 6 to 100

The polyamide of (4);

polyamides corresponding to formula (VI), in which the radicals Y and Y¹At least one of (A) is contained in

At least one hydroxyl substituent;

-synthesis of diacids replaced by at least partially activated diacids (diacid chlorides, dianhydrides or diesters)

A polyamide of formula (III);

wherein X represents- (CH)₂)₃-or- (CH)₂)₁₀A polyamide of formula (III); and

polyamides of formula (III), wherein the polyamide ends in monofunctional chains, these monofunctional chains

The functional chain is selected from monofunctional amines, monofunctional acids, monofunctional alcohols, including fats

Acids, fatty alcohols and fatty amines, such as octylamine, octanol, stearic acid and stearyl alcohol.

According to the invention, the end groups of the polymer chain may end up in:

by introducing C during the synthesis₁-C₅₀C by monohydric alcohol₁-C₅₀Alkyl ester radical

The mass of the balls is obtained by mixing the raw materials,

if the siloxane is α, by using a monobasic acid as a terminating group, or

If the siloxane is α, C of the omega-dicarboxylic acid with a monoamine as the terminating group₁-C₅₀Alkane (I) and its preparation method

A carboxamide group.

According to a variant of one embodiment of the invention, it is possible to use copolymers of silicone polyamides and of hydrocarbon-based polyamides, i.e. copolymers comprising moieties of formula (III) or (IV) and hydrocarbon-based polyamide moieties. In this case, the polyamide-siloxane moiety may be arranged at the end of the hydrocarbon-based polyamide.

The silicone-containing polyamide-based gelling agent may be produced by silylamidation of a polyamide based on a dimer fatty acid. This process involves the reaction of the free acid sites present on the polyamide as terminal sites with organosiloxane-monoamines and/or organosiloxane-diamines (amidation reaction) or with oligomeric siloxanols or oligomeric siloxane diols (esterification reaction). The esterification reaction requires the presence of an acid catalyst, as is well known in the art. For amides containing free acid sites for amidation or esterification reactions, it is desirable to have a higher number of acid end groups (e.g., polyamides with high acid numbers (e.g., 15-20)).

For amidation of the free acid sites of the hydrocarbon-based polyamide, siloxane diamines having 1 to 300, preferably 2 to 50, more preferably 2, 6, 9.5, 12, 13.5, 23 or 31 siloxane groups can be used for the reaction with the hydrocarbon-based polyamide based on fatty acid dimers. Siloxane diamines containing 13.5 siloxane groups are preferred, and the best results are obtained with siloxane diamines containing 13.5 siloxane groups and polyamides with a high number of carboxylic acid end groups.

These reactions can be carried out in xylene to distill off the water produced from the solution by azeotropic distillation, or can be carried out at higher temperatures (about 180-. Typically, the efficacy of the amidation and the reaction rate decrease when the siloxane diamine is longer, that is, when the number of siloxane groups is higher. After the initial amidation reaction of the diamino siloxane, the free amine sites can be blocked by reacting them with a siloxane acid or with an organic acid (e.g., benzoic acid).

For the esterification of the free acid sites on the polyamide, it can be carried out in boiling xylene, with about 1% by weight of p-toluenesulfonic acid as catalyst, relative to the total weight of the reactants.

These reactions, which are carried out at the carboxylic acid end groups of the polyamide, lead to the introduction of siloxane moieties only at the polymer chain ends.

Polyamide-siloxane copolymers can also be prepared by amidation reactions with siloxanes containing acid groups using polyamides containing free amino groups.

Gelling agents based on copolymers between hydrocarbon-based polyamides and silicone polyamides may also be prepared by transamidation of polyamides having, for example, an ethylenediamine component with an oligosiloxane- α, omega-diamine at high temperatures (e.g., 200-.

The copolymer of hydrocarbon-based polyamide and polyamide-siloxane may also be a graft copolymer comprising a hydrocarbon-based polyamide backbone and having pendent oligomeric siloxane groups.

This can be obtained, for example, by the following procedure:

by hydrosilylation of unsaturated bonds in polyamides based on fatty acid dimers

Using;

-by silanization of the amino groups of the polyamide; or

By silanization of unsaturated polyamides by means of oxidation, i.e. by reacting unsaturated polyamides with oxygen

And oxidation of the group to an alcohol or diol to form a reaction with a siloxane carboxylic acid or siloxane alcohol

A hydroxyl group of (a). It is also possible to epoxidize the ethylenic sites of the unsaturated polyamide, and

the epoxy groups may then be reacted with a siloxane diamine or siloxane alcohol.

According to a second embodiment of the invention, the gelling agent consists of a homopolymer or a copolymer comprising urethane or urea groups.

As previously mentioned, the polymer may comprise polyorganosiloxane moieties containing two or more urethane and/or urea groups in the main chain of the polymer or in side chains or as a pendant group.

The polymer comprising at least two urethane and/or urea groups in the main chain may be a polymer comprising at least one moiety corresponding to the formula:wherein R is¹、R²、R³、R⁴X, Y, m and n have the meanings given above for formula (I), U represents-O-or-NH-, and thus:

corresponding to urethane or urea groups.

In the formula (VIII), Y may be a straight or branched C₁-C₄₀Alkylene, optionally with C₁-C₁₅Alkyl or C₅-C₁₀Aryl substitution. It is preferable to use- (CH)₂)₆-a group.

Y may also represent C₅-C₁₂Cycloaliphatic or aromatic radicals, which may be substituted by C₁-C₁₅Alkyl or C₅-C₁₀Aryl-substituted, for example, radicals selected from the group consisting of methylene-4, 4-dicyclohexyl, the radical derived from isophorone diisocyanate, 2, 4-and 2, 6-benzylidene, 1, 5-naphthylene, p-naphthylene and 4, 4' -diphenylenemethane. In general, it is preferred that Y represents a linear or branched chainC₁-C₄₀Alkylene or C₄-C₁₂A cycloalkylene group.

Y may also represent a polyurethane or polyurea block, corresponding to the condensation of several diisocyanate molecules with one or more molecules of coupling agents of the diol or diamine type. In this case, Y contains several urethane or urea groups in the alkylene chain.

It may correspond to the following formula:wherein, B¹Is selected from the groups given above for Y, U is-O-or-NH-, and B²Selected from:

● straight or branched chain C₁-C₄₀Alkylene groups, which may optionally contain ionizable groups, such as carboxylic or sulfonic acid groups, or neutralizable or quaternizable tertiary amine groups,

●C₅-C₁₂cycloalkylene, optionally containing alkyl substituents, for example 1 to 3 methyl or ethyl groups, or alkylene, such as diol groups: the cyclohexane dimethanol compound is a compound of cyclohexane dimethanol,

● may optionally contain C₁-C₃Phenylene with an alkyl substituent, and

● A group of the formula:wherein T is a trivalent hydrocarbon-based radical possibly containing one or more heteroatoms such as oxygen, sulphur and nitrogen, R⁵Is a polyorganosiloxane chain or a linear or branched C₁-C₅₀An alkyl chain.

For example, T may represent:

orw is an integer of 1 to 10, R⁵Is a polyorganosiloxane chain.

When Y is straight or branched C₁-C₄₀When alkylene is- (CH)₂)₂-and- (CH)₂)₆The group is preferred.

In the formulae given above for Y, d may be an integer from 0 to 5, preferably from 0 to 3, more preferably equal to 1 to 2.

Preferably, B²Is straight-chain or branched C₁-C₄₀Alkylene, especially- (CH)₂)₂-or- (CH)₂)₆-or the group:wherein R is⁵Is a polyorganosiloxane chain.

As previously mentioned, the polymers that make up the gelling agent may be formed from silicone urethane and/or silicone urea moieties of varying lengths and/or compositions, and may be in the form of block copolymers or random copolymers.

According to the invention, the siloxanes may also comprise urethane groups and/or urea groups no longer in the main chain but as side chains.

In this case, the polymer may comprise at least one moiety having the formula:wherein R is¹、R²、R³、m₁And m₂Having the meanings given above for formula (I),

-U represents O or NH,

-R²³is represented by C₁-C₄₀Optionally containing one or more groups selected from O and N

Or represents phenylene, and

-R²⁴selected from linear, branched or cyclic, saturated or unsaturated C₁-C₅₀Alkyl, and

selecting 1-3C₁-C₃Alkyl-substituted phenyl.

The polymers comprising at least one moiety of formula (X) contain siloxane units and urea or urethane groups and they may be used as gelling agents in the compositions of the invention.

The siloxane polymers may have a single urea or urethane group by branching, or may have branches containing two urea or urethane groups, or they may comprise a mixture of branches containing one urea or urethane group and branches containing two urea or urethane groups.

They can be obtained from branched polysiloxanes containing one or two amino groups by branching, even if these polysiloxanes are reacted with a monoisocyanate.

As examples of starting polymers of this type containing amino and diamino branches, mention may be made of polymers corresponding to the formula:

in these formulae, the symbol "/" indicates that the moieties may be of different lengths and in random order, and R represents a straight chain aliphatic group, preferably containing 1 to 6 carbon atoms, preferably containing 1 to 3 carbon atoms.

Such polymers containing branches can be formed by reacting a siloxane polymer containing at least 3 amino groups per polymer molecule with a compound containing only one monofunctional group (e.g., an acid, isocyanate, or isothiocyanate) so that the monofunctional group reacts with one of the amino groups and forms a group capable of establishing a hydrogen interaction. The amino group may be on a side chain extending from the main chain of the siloxane polymer so that a group capable of establishing hydrogen interaction is formed on these side chains, or the amino group may be at the end of the main chain so that a group capable of establishing hydrogen interaction becomes the terminal group of the polymer.

As a process for forming a silicone-containing polymer containing siloxane units and groups capable of establishing hydrogen interactions, the reaction of a siloxane diamine with a diisocyanate in a siloxane solvent to directly provide a gel may be mentioned. The reaction may be carried out in a silicone fluid, the resulting product being dissolved in the silicone fluid at an elevated temperature, and the temperature of the system then being reduced to form a gel.

Preferred polymers for incorporation into the compositions according to the invention are siloxane-urea copolymers which are linear and contain urea groups as groups capable of establishing hydrogen interactions in the main chain of the polymer.

As an example of a polysiloxane ending with 4 urea groups, mention may be made of polymers having the formula:

where Ph is phenyl and n is a number from 0 to 300, in particular from 0 to 100, for example 50.

This polymer is obtained by reacting the following amino group-containing polysiloxane with phenyl isocyanate:

the polymers of formula (VIII) comprising urea groups or urethane groups in the siloxane polymer backbone may be prepared by polymerizing a siloxane polymer containing α, omega-NH groups of the formula₂or-OH-terminated siloxanes and diisocyanatesOCN-Y-NCO (Y has the meaning given in formula (I)) and optionally of the formula H₂N-B²-NH₂Or HO-B²Diol or diamine coupling agents of-OH (where, B²As defined by formula (IX) to obtain:wherein, m and R¹、R²、R³、R⁴And X is as defined for formula (I).

Depending on the stoichiometric ratio between the two reactants, i.e. the diisocyanate and the coupling agent, Y may have the formula (IX), d being equal to 0 or d being equal to 1 to 5.

As in the case of the polyamidosiloxanes of the formula (II) or (III), it is possible in the present invention to use polyurethane or polyurea silicones which comprise moieties having different lengths and structures, in particular moieties whose length differs by the number of siloxane units. In this case, for example, the copolymer may correspond to the formula:wherein R is¹、R²、R³、R⁴X, Y and U are as defined for formula (VIII), m₁、m₂N and p are as defined for formula (V).

Branched polyurethane or polyurea siloxanes can also be obtained using triisocyanates of the formula in place of the diisocyanate OCN-Y-NCO:

thus obtaining a mixture containing a compound capable of establishing hydrogen interactionsBranched polyurethane or polyurea siloxanes of organosiloxane chains of the group. For example, such polymers comprise moieties corresponding to the formula:wherein, X¹And X²Are identical or different and have the meaning given for X in formula (I), n is as defined for formula (I), Y and T are as defined for formula (I), R¹¹-R¹⁸Is selected from the group consisting of¹-R⁴Same group, m₁And m₂Is a number in the range of 1 to 1000 and p is an integer in the range of 2 to 500.

As in the case of polyamides, such copolymers may also contain polyurethane silicone moieties without branching.

In this second embodiment of the invention, the preferred silicone-based polyureas and polyurethanes are:

-polymers of formula (III) wherein m is 15 to 50;

-wherein at least one polymer has a value of m of 15 to 50 and at least one polymer has a value of m

A mixture of two or more polymers having a value of 30 to 50;

-polymers of formula (XII), m₁Selected in the range of 15-50, m₂At 30-500

Selected within the range, having m₁In a corresponding proportion of 1 to 99 parts by weight based on the total weight of the polymer

Amount% and m₂In a corresponding proportion of from 1 to 99% by weight, based on the total weight of the polymer;

-a mixture of polymers of formula (VIII) combining:

1)80 to 99% by weight of a polymerization in which n is equal to 2 to 10, in particular 3 to 6

An object, and

2)1 to 20% by weight of a compound in which n is in the range from 5 to 500, in particular 6 to 100

The polymer of (a);

-a copolymer comprising two moieties of formula (VIII), wherein at least one of the groups Y

Containing at least one hydroxyl substituent;

A polymer of formula (VIII);

wherein X represents- (CH)₂)₃-or- (CH)₂)₁₀A polymer of formula (VIII); and

polymers of formula (VIII), in which the polyamide terminates in a multifunctional chain, such a polymer

The functional chain is selected from the group consisting of monofunctional amines, monofunctional acids, monofunctional alcohols, including esters

Fatty acids, fatty alcohols and fatty amines, such as octylamine, octanol, stearic acid and stearyl alcohol.

Copolymers of polyurethane or polyurea siloxanes and hydrocarbon-based polyurethanes or polyureas can be used in the present invention, as in the case of polyamides, by carrying out the reaction of the synthetic polymer in the presence of α, omega-difunctional block terminals (such as polyesters, polyethers or polyolefins) having non-silicone properties.

From the foregoing, it can be seen that the gelling agent composed of the homopolymer or copolymer of the present invention may comprise a siloxane moiety in the main chain of the polymer and a group capable of establishing hydrogen interaction in the main chain of the polymer or at the terminal thereof, or on a side chain or branch of the main chain. This may correspond to the following five permutations:

wherein the solid line is the main chain of the siloxane polymer and the squares represent groups capable of establishing hydrogen interactions.

In the case (1), groups capable of establishing hydrogen interactions are arranged at both ends of the main chain. In the case (2), two groups capable of establishing hydrogen interaction are arranged at each of both ends of the main chain.

In the case (3), the groups capable of establishing hydrogen interactions are arranged within the main chain in the form of repeating portions.

In the cases (4) and (5), these are copolymers in which the groups capable of establishing hydrogen interactions are arranged on branches of the main chain of the moiety of the first series which is copolymerized with the moiety free of groups capable of establishing hydrogen interactions. The values n, x and y make the polymer have the desired properties with respect to the agent for gelling the fatty phase based on silicone oil.

According to the invention, with the aid of one or more of the above-mentioned polymers, a structuring of a liquid fatty phase containing at least one silicone oil and comprising a volatile silicone oil or volatile non-silicone oil having a flash point greater than or equal to 40 ℃ and higher than the softening point of the gelling polymer, preferably greater than 60 ℃, more preferably greater than 80 ℃, is obtained.

Mention may be made, as examples of polymers that can be used, of the silicone polyamides obtained according to examples 1 and 2 of document US-A-5981680.

The polymers and copolymers used as gelling agents in the compositions of the present invention advantageously have a softening point of from 40 to 190 ℃. Preferably, they have a softening point of from 50 to 140 ℃ and more preferably from 70 to 120 ℃. This softening point is lower than that of the known structuring polymers, which facilitates the application of the polymers object of the present invention, and it is possible to use volatile oils having a flash point higher than the softening point of the polymers, and limit the deterioration of the liquid fatty phase.

By selecting the gelling polymer and the volatile oil, respectively, with a softening point and a flash point within the above ranges, any risk of explosion during the introduction of the gelling polymer into the composition is avoided. In particular, the gelling polymer may melt at a temperature lower than that at which the volatile oil is at risk of ignition.

Therefore, in the present invention, the gelling polymer and the volatile oil are selected so as to satisfy the above-mentioned conditions.

The gelling polymer has good solubility in silicone oils and results in macroscopically homogeneous compositions. Preferably, they have an average molecular weight of 500-.

According to the invention, the hardness of the composition is preferably from 20 to 2000gf, more preferably from 20 to 900gf, particularly preferably from 20 to 600gf, for example from 150-450 gf.The hardness may be based on probe penetrationThe composition is measured by the method, in particular in a texture analyser equipped with a hard rubber cylinder 25 mm high and 8 mm in diameter (for example TA-TXT2 from Rheo)_i) With the help of (1). Hardness measurements were performed at 20 ℃ in 5 sample centers of the composition. The cylinder was introduced into each sample of the composition at a pre-speed of 2 mm/sec, then at a speed of 0.5 mm/sec, and finally at a post-speed of 2 mm/sec for a total displacement of 1 mm. The hardness values recorded are the maximum peak values. The measurement error was. + -. 50 gf.

Hardness can also be measured by the "cheese wire" method, which involves moving at 100 mm/min using a DFGHS 2 tensile tester from Inpelco-Chatillon, cutting a 8.1 mm diameter lipstick tube and measuring the hardness at 20 ℃. It is expressed as the shear force (expressed in grams force) required to cut the lipstick strip under these conditions. According to this method, the hardness of the bar composition according to the invention is from 30 to 300gf, preferably from 30 to 200gf, for example from 30 to 120 gf.

The hardness of the composition according to the invention is such that the composition is self-supporting and can be easily separated in order to form a satisfactory attachment to the skin and lips. Furthermore, with this hardness, the compositions of the invention exhibit good impact strength.

According to the invention, the composition in strip form has the property of a deformable and soft elastic solid, obtaining a noteworthy elastic softness upon application. The prior art bar compositions do not have such elastic and flexible properties.

The polymer content is selected according to the desired gel hardness and according to the specific application. The polymer content must be such that an easily separable strip can be obtained. In practice, the amount of polymer (on an active material basis) is from 0.5% to 80%, preferably from 5% to 40% by weight of the total composition.

The compositions of the invention may also comprise any ingredient commonly used in the field considered, in particular those selected from dyes soluble in the polyol or fatty phase, antioxidants, essential oils, preservatives, fragrances, liposoluble polymers, especially hydrocarbon-based liposoluble polymers such as polyalkylene or polyvinyl laurate, liquid fatty phase gelling agents, waxes, gums, resins, surfactants such as triolein phosphate, additional cosmetic or dermatological active agents such as water, emollients, moisturizers, vitamins, liquid lanolin, essential fatty acids, liposoluble sunscreens or opacifiers soluble in polyols, and mixtures thereof. The composition according to the invention may also comprise lipid vesicles of ionic and/or non-ionic type. In addition to water, these ingredients may also be present in the composition in the usual manner, in proportions of from 0 to 20%, preferably from 0.1 to 10%, by weight of the total composition.

In the case of compositions comprising an aqueous phase, i.e. a water-in-oil or oil-in-water simple emulsion or a water-in-oil-in-water or oil-in-water-in-oil-in-water multiple emulsion, this aqueous phase may represent from 0.1 to 70%, in particular from 0.5 to 40%, preferably from 1 to 20%, of the total weight of the composition. This aqueous phase may contain water and any water-miscible compound, such as a polyol. This aqueous phase may also be gelled with a suitable gelling agent. Preferably, the composition of the invention is in the form of a continuous fatty phase, in particular in anhydrous form.

Needless to say, the person skilled in the art will take care to select the optional additional ingredients and/or the amounts thereof such that the additions encountered do not or substantially do not adversely affect the beneficial properties of the composition according to the invention.

The composition of the invention may in particular contain one or more waxes, for example polyethylene waxes, but the use of waxes is avoided if it is desired to obtain glossy articles. Generally, the amount of wax used is not more than 20%, preferably not more than 10%, for example 3-5% by weight of the total composition.

The compositions according to the invention may be in the form of optionally pigmented skin or care compositions for keratin materials such as the skin, lips and/or coverings, in the form of sun protection compositions or body hygiene compositions, in particular in the form of off-loading products in the form of strips. It can be used in particular as a care base for the skin, a covering or the lips (lipstick, for protecting the lips against cold and/or sunlight and/or wind, or a care cream for the skin, the nails or the hair).

The composition of the invention can also be a coloured cosmetic preparation for the skin, in particular a foundation, optionally with care and treatment properties, a blusher, a face powder, an eye shadow, a concealer, an eyeliner or a cosmetic preparation for the body; lip makeup, such as lipstick, optionally with care or treatment properties; for making up coverings such as nails or eyelashes, in particular in the form of a mascara cake, or for making up eyebrows and hair, in particular in the form of a pen. In particular, the compositions of the invention may be cosmetic preparations containing cosmetic and/or dermatological active agents such as moisturizers, ceramides, vitamins, sunscreens or healing agents.

In the case of cosmetic compositions, the hydrophobic or hydrophilic solid particles may constitute the pigment(s) used for making up the skin, the lips and/or the covering.

It goes without saying that the composition of the invention must be cosmetically or dermatologically acceptable, i.e. it must contain a non-toxic physiologically acceptable medium which can be applied to the skin, the integuments or the lips of a human being. For the purposes of the present invention, the expression "cosmetically acceptable" means a composition having a pleasant appearance, smell, sensation and possibly taste.

Moreover, the makeup or care composition according to the invention must comprise at least 10% by weight of non-volatile oils (silicone oils or non-silicone oils) and/or pasty fatty substances, i.e. viscous products containing a liquid fraction and a solid fraction.

For the purposes of the present invention, the expression "pasty fatty substance" means a fatty substance having a melting point of between 20 and 55 ℃, preferably between 25 and 45 ℃, and/or a viscosity of between 0.1 and 40 pas (1 and 400 poises), preferably between 0.5 and 25 pas, at 40 ℃ measured with a Contraves TV or Rheomat 80 viscometer equipped with a spindle rotating at 60 Hz. The person skilled in the art can select, on the basis of his general knowledge, a spindle for measuring the viscosity from among the spindles MS-r3 and MS-r4, in order to be able to measure the viscosity of the pasty compound tested.

According to the invention, the melting point value corresponds to the melting peak measured by "differential scanning calorimetry" with a heating rate of 5 or 10 ℃/min.

According to the invention, one or more pasty fatty substances may be used. Preferably, these fatty substances are hydrocarbon-based compounds (mainly containing carbon and hydrogen atoms and possible ester groups), optionally polymeric; they may also be chosen from silicones and/or fluorine-containing compounds; they may also be in the form of mixtures of hydrocarbon-based compounds and/or siloxane compounds. In the case of mixtures of different pasty fatty substances, it is preferable to use the pasty hydrocarbon-based compounds in a predominant proportion.

Among the pasty compounds which can be used in the compositions according to the invention, mention may be made of lanolin and lanolin derivatives, such as acetylated lanolin or oxyalkylenated lanolin or isopropyl lanolate, having a viscosity of from 18 to 21 pas, preferably from 19 to 20.5 pas, and/or a melting point of from 30 to 55 pas, and mixtures thereof. Esters of fatty acids or of fatty alcohols, in particular those containing from 20 to 65 carbon atoms (melting point about 20 to 35 ℃ and/or viscosity at 40 ℃ of from 0.1 to 40 pas), such as triisostearoyl citrate or cetyl citrate; arachidyl propionate; polyvinyl laurate; cholesterol esters, for example triglycerides of vegetable origin such as hydrogenated vegetable oils, viscous polyesters such as poly (12-hydroxystearic acid) and mixtures thereof. Triglycerides of vegetable origin that may be used include hydrogenated castor oil derivatives such as "THIXINR" from Rheox.

Mention may also be made of pasty fatty substances based on silicones, such as Polydimethylsiloxanes (PDMSs) which contain pendant chains of the alkyl or alkoxy type containing from 8 to 24 carbon atoms and which have a melting point of from 20 to 55 ℃, for example stearoyldimethicone, in particular those sold by the company Dow Corning under the trade names DC2503 and DC25514, and mixtures thereof.

The proportion of pasty fatty substance(s) is 0.5 to 60% by weight, preferably 2 to 45% by weight, more preferably 5 to 30% by weight, relative to the total weight of the composition.

According to the invention, the composition may be in the form of a transparent anhydrous rigid gel, in particular in the form of a transparent anhydrous stick, without the presence of diffusing particles (such as certain fillers and pigments).

According to the invention, the composition may also contain a dye which may be chosen from lipophilic dyes and hydrophilic dyes and mixtures thereof.

Liposoluble dyes are, for example, Sudan red (Sudan red), DC Red No. 17, DC Green No. 6, β -carotene, soybean oil, Sudan brown (Sudan brown), DC yellow No. 11, DC Violet No. 2, DC orange No. 5, quinoline yellow and carmine, which may be present in an amount of 0-20%, preferably 0.1-6%, by weight of the composition.

The composition according to the present invention can be manufactured by a known method commonly used in cosmetic makeup or dermatology. It can be manufactured by heating the polymer at least to its softening point, adding the oil(s), if desired the amphiphilic compound(s), the dye(s) and/or the solid particles and the additives thereto, and then mixing all until a homogeneous solution is obtained, which is observed by the naked eye. The resulting homogeneous mixture is then injected into a suitable mould, such as a lipstick mould, or directly into the package (in particular a box or tray).

Another object of the present invention is a cosmetic care, makeup or treatment method for human keratin materials, in particular the skin, the lips and the integuments, comprising the application to the keratin materials of the composition, in particular the cosmetic composition defined above.

Another object of the present invention is the use of a sufficient amount of at least one polymer (homopolymer or copolymer) in a cosmetic composition or in the manufacture of a physiologically acceptable composition comprising a liquid continuous fatty phase comprising at least one silicone oil, the liquid fatty phase being partially or totally composed of a volatile oil (or volatile oils) having a flash point greater than or equal to 40 ℃ and higher than the softening point of the gelling polymer,

with the proviso that the composition comprises at least 10% by weight of a non-volatile oil and/or a pasty or viscous product, so that the composition is structured in the form of a self-supporting solid having a hardness of from 20 to 2000gf, preferably from 20 to 900gf, more preferably from 20 to 600gf, the weight average molecular weight of the polymer being from 500-500000 and containing at least one moiety comprising:

at least one polyorganosiloxane group, consisting of in the chain of the moiety or in the form of a graft

From 1 to 1000 organosiloxane units of the formula, and

-at least two groups capable of establishing hydrogen interactions, selected from esters, amides, sulfonamides,

Carbamates, thiocarbamates, ureas, thioureas, oxamido, guanidino,

And bis-guanidino groups and combinations thereof, provided that at least one of the groups is not an ester group, the polymer being solid at room temperature and soluble in said liquid fatty phase at a temperature of from 25 to 250 ℃.

Another subject of the present invention is the use of a continuous liquid fatty phase comprising at least one silicone oil, substantially structured with a sufficient amount of at least one polymer (homopolymer or copolymer) having a weight-average molecular weight of 500-500000, comprising at least one moiety comprising:

From 1 to 1000 organosiloxane units of the formula, and

Carbamates, thiocarbamates, ureas, thioureas, oxamido, guanidino,

And biguanide groups and combinations thereof, with the proviso that at least one of the groups is not an ester group, which polymer is solid at room temperature and soluble in the liquid fatty phase at a temperature of from 25 to 250 ℃, said liquid fatty phase consisting partly or totally of a volatile oil (or volatile oils) having a flash point greater than or equal to 40 ℃ and higher than the softening point of the gelling polymer.

Another object of the present invention is the use of a sufficient amount of at least one polymer (homopolymer or copolymer) in a cosmetic composition or in the manufacture of a physiologically acceptable composition comprising a liquid continuous fatty phase comprising at least one silicone oil, consisting partially or totally of a volatile oil (or oils) having a flash point greater than or equal to 40 ℃ and higher than the softening point of the gelling polymer, with the proviso that the composition comprises at least 10% by weight of a non-volatile oil and/or of a pasty or viscous product, so as to structure the composition in a self-supporting form, the polymer having a weight-average molecular weight of 500-500000 and comprising at least one moiety comprising:

From 1 to 1000 organosiloxane units of the formula, and

Carbamates, thiocarbamates, ureas, thioureas, oxamido, guanidino,

The invention also relates to the use of a continuous liquid fatty phase containing at least one silicone oil, substantially structured with a sufficient amount of at least one polymer (homopolymer or copolymer) having a weight-average molecular weight of 500-500000, containing at least one moiety comprising:

1-1000 organosiloxane unit compositions of formula (la), and

Carbamates, thiocarbamates, ureas, thioureas, oxamido, guanidino,

And biguanide groups and combinations thereof, with the proviso that at least one of the groups is not an ester group, the polymer being solid at room temperature and soluble at a temperature of from 25 to 250 ℃ in said liquid fatty phase consisting partly or totally of a volatile oil (or oils) having a flash point greater than or equal to 40 ℃ and higher than the softening point of the gelling polymer.

Another subject of the present invention is a cosmetic makeup method for limiting the migration of a cosmetic composition comprising a liquid fatty phase comprising at least one silicone oil, which comprises structuring said fatty phase with a sufficient amount of at least one polymer (homopolymer or copolymer) having a weight-average molecular weight of 500-500000 comprising at least one moiety comprising:

From 1 to 1000 organosiloxane units of the formula, and

Carbamates, thiocarbamates, ureas, thioureas, oxamido, guanidino,

And biguanide groups and combinations thereof, with the proviso that at least one of the groups is not an ester group, which polymer is solid at room temperature and soluble at a temperature of from 25 to 250 ℃ in the liquid fatty phase consisting partly or totally of a volatile oil (or volatile oils) having a flash point greater than or equal to 40 ℃ and greater than the softening point of the gelling polymer, with the proviso that the composition comprises at least 10% by weight of a non-volatile oil and/or a pasty or viscous product.

Another object of the present invention is a cosmetic strip for the skin, lips and/or integuments, in particular for the lips, comprising at least one pigment and a liquid continuous fatty phase in an amount sufficient to make up the skin, lips and/or integuments, structured with at least one polymer (homopolymer or copolymer) having a weight average molecular weight of 500-500000, comprising at least one moiety comprising:

From 1 to 1000 organosiloxane units of the formula, and

Carbamates, thiocarbamates, ureas, thioureas, oxamido, guanidino,

The pigment, fatty phase and polymer form a physiologically acceptable medium.

Detailed Description

The invention is illustrated in more detail in the following examples of cosmetic formulations containing silicone polyamides and pigments and/or fillers having hydrophobic surfaces. The amounts are given in mass percent. The compounds are given primarily by the CTFA name ("International Cosmetic ingredient dictionary"). The indicated viscosities are determined at 25 ℃ and atmospheric pressure.

Example 1: lipstick

Composition of
Composition of		PDMS-DC 200(5 cSt) Cyclohexasiloxane D6 Phenyltrimethicone (DC 556, 20 from Dow Corning) cSt) Hydrogenated isoparaffin (Parleam @, from Nippon Oil falls) Hydrophobically treated pigments (red and yellow iron and titanium oxides, with phosphorus) Acid perfluoroalkyl ester treated) Polyethylene wax (Performalen 500 from Petrolite) Silicone Polyamide of example 1 of patent US 5981680 Proper amount of preservative Proper amount of perfume	Proper amount is 100% 20％ 12％ 5％ 10％ 12％ 15％

The pigment has the following Color Index (CI):

red iron oxide CI: 77491

Yellow iron oxide CI: 77492

Titanium oxide CI: 77891

This lipstick was obtained by heating the wax and the polymer to the melting point of the mixture, then adding Parleam and a portion of the phenyl trimethicone. The pigment and the other part of the phenyltrimethicone were separately mixed together at room temperature and then milled in a three-roll mill. This ground material is added to a molten mixture of wax and silicone oil, and the whole is then homogenized. The mixture is cooled at least 20 ℃ relative to the melting point of the mixture with continuous stirring, followed by addition of cyclohexasiloxane D6 and polydimethylsiloxane 5cSt, followed by addition of preservatives and fragrance. The mixture is then injected into a suitable mold.

The resulting product has retention properties, especially color retention, and is smooth and non-greasy.

Example 2: lipstick

Composition of
Composition of		PDMS-DC 200(3 cSt) α -omega oxyethylene/oxypropylene in cyclopentasiloxane D5 PDMS (Abil EM90 from Goldschmidt) Phenyltrimethicones from Dow Corning DC 556, 20 cSt) Hydrogenated isoparaffin (Parleam @, from Nippon Oil falls) Pigments (Red, yellow and brown iron and titanium oxides) Polyethylene wax (Performalen 500 from Petrolite) Silicone Polyamide of example 1 of patent US 5981680 Proper amount of preservative Proper amount of perfume	Proper amount is 100% 3％ 12％ 5％ 10％ 12％ 15％

The pigment has the following Color Index (CI):

red iron oxide CI: 77491

Yellow iron oxide CI: 77492

Brown iron oxide CI: 77491

Titanium oxide CI: 77891

This lipstick was obtained by heating the wax and the polymer to the melting point of the mixture, then adding Parleam and a portion of the phenyl trimethicone. The pigment, Abil EM90, and the other portion of phenyltrimethicone were separately mixed together at room temperature and then milled in a three-roll mill. This ground material is added to a molten mixture of wax and silicone oil, and the whole is then homogenized. The mixture is cooled at least 20 ℃ relative to the melting point of the mixture under continuous stirring, then polydimethylsiloxane 3cSt is added, followed by preservatives and fragrances. The mixture is then injected into a suitable mold.

In examples 1 and 2, the siloxane polyamide used contained 30 units of [ Si (CH)₃)₂-O]. When using [ Si (CH) of the siloxane polyamides of comparative examples 1 and 2₃)₂-O]With fewer units, a softer, less glossy gel was obtained. In fact, when the [ Si (CH) of the polymer₃)₂-O]As the number of units increases, a harder and glossier gel is obtained.

Example 3: anhydrous foundation

Composition of
Composition of		PDMS (5 cSt) DC 200(5 cSt) from Dow Corning Phenyl trimethicone (DC 556) PDMS(300 cSt) Hydrophobically treated pigments (red, yellow and brown iron oxides and oxides) Titanium, treated with a perfluoroalkyl phosphate) Polyethylene wax (Performalen 500) Silicone Polyamide of example 2 of patent US 5981680 Hydrophobically treated silica (trimethylsiloxy treatment) Isononyl isononanoate Isohexadecane Proper amount of preservative Proper amount of perfume	Proper amount is 100% 12％ 5％ 10％ 15％ 12％ 3％ 10％ 10％

This foundation was prepared as the lipstick of example 1, incorporating the silica at the same time as the phenyltrimethicone was incorporated into the ground pigment, isononyl isononanoate was incorporated into the mixture of wax and silicone oil, and isohexadecane was incorporated simultaneously with the cyclohexasiloxane.

It has the properties of non-greasy, smooth and matt effect and has good staying power over time, in particular colour staying power.

The particles used are hydrophobic particles (or more preferably lipophilic particles).

Cited reference [1] EP-A-1068856[ 2] US-A-5874069[ 3] US-A-5919441[ 4] US-A-6051216[ 5] US-A-5981680[ 6] US-A-5412004[ 7] EP-A-1048686[ 8] WO-A-02/17870[9] WO-A-02/17871

Claims

1. Composition comprising a liquid fatty phase containing at least one silicone oil, structured with at least one gelling agent consisting of a polymer (homopolymer or copolymer) with a weight-average molecular weight of 500-500000, which contains at least one moiety comprising:

From 1 to 1000 organosiloxane units of the formula, and

Carbamates, thiocarbamates, ureas, thioureas, oxamido, guanidino,

And biguanide groups, and combinations thereof, with the proviso that at least one of the groups is not an ester group, the polymer being solid at room temperature and soluble at 25-250 ℃ in said liquid fatty phase consisting partly or totally of a volatile oil (or oils) having a flash point greater than or equal to 40 ℃ and above the softening point of the gelling polymer, said liquid fatty phase and polymer forming a physiologically acceptable medium.

2. Composition according to claim 1, in which the fatty phase is a mixture of oils comprising at least one non-volatile silicone oil and at least one volatile silicone oil having a flash point greater than or equal to 40 ℃ and higher than the softening point of the gelling polymer.

3. Composition according to claim 2, in which the liquid fatty phase comprises at least one non-volatile non-silicone oil.

4. Composition according to claim 1, in which the fatty phase consists solely of volatile silicone oil(s) having a flash point greater than or equal to 40 ℃ and higher than the softening point of the gelling polymer.

5. The composition according to claim 2 or 3, wherein the volatile oil is a silicone oil.

6. The composition according to claim 2 or 3, wherein the volatile oil is a non-silicone oil.

7. Composition according to claim 2 or 3, in which the mixture comprises at least one volatile silicone oil and at least one volatile non-silicone oil having a flash point greater than or equal to 40 ℃ and higher than the softening point of the gelling polymer.

8. Composition according to any one of claims 4, 5 and 7, in which the volatile silicone oil is chosen from the following compounds: octyltrimethicone, hexyltrimethicone, octamethylcyclotetrasiloxane D4, dodecamethylcyclohexasiloxane D6, heptamethyloctyltrisiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxane, 1.5 cSt polydimethylsiloxane, 2cSt polydimethylsiloxane, 3cSt polymethylsiloxane, 5cSt polydimethylsiloxane, and mixtures thereof.

9. Composition according to either of claims 6 and 7, in which the non-silicone volatile oil is chosen from the following compounds: isododecane, isohexadecane, C₈-C₁₆Isoparaffins, isodecyl neopentanoate, propylene glycol n-butyl ether, ethyl 3-ethoxypropionate, propylene glycol methyl ether acetate, isohexyl neopentanoate, and mixtures thereof.

10. Composition according to any one of the preceding claims, characterized in that the flash point of the volatile oil is greater than 60 ℃, preferably greater than 80 ℃, more preferably greater than 93 ℃.

11. Composition according to any one of the preceding claims, characterized in that the flash point of the volatile oil is less than or equal to 160 ℃, preferably less than or equal to 135 ℃.

12. Composition according to any one of the preceding claims, in which the liquid fatty phase contains at least 40%, preferably at least 50% by weight of silicone oil.

13. Composition according to any one of the preceding claims, in which the volatile oil represents from 3% to 89.4% by weight of the total composition.

14. A composition according to any one of the preceding claims, further comprising a dye.

15. The composition according to any one of claims 1 to 14, further comprising solid particles selected from fillers and pigments and mixtures thereof.

16. The composition of claim 15, wherein the solid particles are hydrophobic particles.

17. The composition of claim 15, wherein the solid particles are hydrophilic particles coated with a hydrophobic compound membrane.

18. The composition of claim 15, wherein the solid particles are hydrophilic particles and the composition further comprises an amphiphilic silicone.

19. The composition according to any one of claims 18-15, wherein the particles are pigments selected from the group consisting of zinc oxide, iron oxide and titanium oxide, and mixtures thereof.

20. A composition according to any one of claims 1 to 19, wherein the polymer used as gelling agent comprises at least one moiety corresponding to the formula:

wherein:

A group, possibly containing in its chain one or more oxygen, sulphur and/or nitrogen atoms,

and may be partially or fully substituted with fluorine atoms,

polyorganosiloxanes which may contain one or more oxygen, sulfur and/or nitrogen atoms

A chain;

2) the X groups, which may be identical or different, represent a linear or branched C₁-C₃₀Alkylene diyl (alkylene), possibly containing in its chain one or more oxygen and/or nitrogen atoms;

3) y is saturated or unsaturated C₁-C₅₀Linear or branched divalent alkylene, arylene, cycloalkylene, alkylarylene or arylalkylene groups, possibly comprising one or more oxygen, sulphur and/or nitrogen atoms, and/or bearing as substituents one of the following atoms or groups of atoms:

fluorine, hydroxy, C₃-C₈Cycloalkyl radical, C₁-C₄₀Alkyl radical, C₅-C₁₀Aryl, optionally 1-3C₁-C₃Alkyl-substituted phenyl, C₁-C₃Hydroxyalkyl and C₁-C₆Aminoalkyl, or

4) Y represents a group corresponding to the formula:

wherein:

Atom, and

Or sulfonamide groups, which may be attached to another chain of the polymer;

21. The composition of claim 20, wherein Y represents a group selected from the group consisting of:

b)C₁₀-C₅₆branched alkylene groups, which may contain cyclic and nonconjugated unsaturation,

c)C₅-C₆a cyclic alkylene group,

d) optionally use oneA plurality of C₁-C₄₀An alkyl-substituted phenylene group, a phenylene group substituted with an alkyl group,

g) polyorganosiloxane chains having the formula:

wherein R is¹、R²、R³、R⁴T and m are as defined above,

22. a composition according to any one of claims 1 to 19, wherein the polymer used as gelling agent contains at least one moiety corresponding to the following formula (II):

wherein:

-R¹and R³May be the same or different and is as defined above for formula (I)

In the above-mentioned manner,

-R⁷is represented by the above pair R¹And R³A group as defined, or of the formula-X-G-R⁹Of (2) a

Wherein X and G are as defined above for formula (I) and R⁹Represents a hydrogen atom

Or C is linear, branched or cyclic, saturated or unsaturated₁-C₅₀Based on hydrocarbon radicals

A group, optionally containing in its chain one or more atoms selected from O, S and N, optionally

Substituted by one or more fluorine atoms and/or one or more hydroxyl groups, or optionally with a group

A plurality of C₁-C₄A phenyl group substituted with an alkyl group,

-m₁is an integer of 1 to 998, and

-m₂is an integer from 2 to 500.

23. The composition of claim 20, wherein the polymer comprises at least one moiety of formula (III) or (IV):or

Wherein R is¹、R²、R³、R⁴X, Y and n are as defined in claim 20.

24. A composition according to either of claims 20 and 21, wherein X and/or Y represent an alkylene group containing in its alkylene moiety at least one of the following:

1 °)1 to 5 amide, urea or urethane groups,

2°)C₅-C₆cycloalkyl radicals, and

3 ℃) optionally with 1 to 3 identical or different C₁-C₃An alkyl-substituted phenylene group, a phenylene group substituted with an alkyl group,

and/or phenylene substituted with at least one member selected from the group consisting of:

-a hydroxyl group,

-C₃-C₈a cycloalkyl group,

1-3 of C₁-C₄₀An alkyl group, a carboxyl group,

optionally 1-3C₁-C₃A phenyl group substituted with an alkyl group,

-C₁-C₃hydroxyalkyl radicals, and

-C₁-C₆an aminoalkyl group.

25. A composition according to any one of claims 20 to 23, wherein Y represents:

wherein R is⁵Represents a polyorganosiloxane chain and T represents a group having the formula:whereinA, b and c are each independently an integer of 1 to 10, R¹⁰Is a hydrogen atom or a group, as in claim 20, R¹、R²、R³And R⁴Those groups as defined.

26. The composition according to any one of claims 20-23, wherein R¹、R²、R³And R⁴Each independently represents a straight or branched C₁-C₄₀Alkyl, preferably CH₃、C₂H₅、n-C₃H₇Or an isopropyl group; polyorganosiloxane chains or phenyl groups optionally substituted with 1-3 methyl or ethyl groups.

27. The composition of claim 1, wherein the polymer used as gelling agent comprises at least one moiety having the formula:

wherein, X¹And X²Which may be identical or different and have the meaning assigned to X in claim 20, n, Y and T being as defined in claim 20, R¹¹-R¹⁸R selected from the group consisting of¹-R⁴Same group, m₁And m₂Is a number from 1 to 1000 and p is an integer from 2 to 500.

28. The composition according to claim 27, wherein:

p is 1 to 25, preferably 1 to 7,

-R¹¹-R¹⁸is a methyl group, and the compound is,

-T corresponds to one of the following formulae:

wherein R is¹⁹Is a hydrogen atom or is selected from the group consisting of p-R¹-R⁴Defined group, R²⁰、R²¹And R²²Each independently a linear or branched alkylene group, more preferably corresponding to the formula:

R²⁰、R²¹and R²²In particular represents-CH₂-CH₂-，

-m₁And m₂In the range of 15 to 500, preferably 15 to 45,

-X¹and X²Is represented by- (CH)₂)₁₀-, and

-Y represents-CH₂-。

29. The composition of any of claims 1-19, wherein the polymer comprises at least one moiety corresponding to the formula:wherein R is¹、R²、R³、R⁴X, Y, m and n have the meanings given above for formula (I) in claim 20, U represents-O-or-NH-, or

Y represents C₅-C₁₂Cycloaliphatic or aromatic radicals, which may be substituted by C₁-C₁₅Alkyl or C₅-C₁₀Aryl-substituted, e.g. selected from methylene-4, 4-dicyclohexyl, radicals derived from isophorone diisocyanate, 2, 4-and 2, 6-benzylidene, 1, 5-naphthylene, p-naphthylene and4, 4' -diphenylenemethane or Y represents a straight-chain or branched C₁-C₄₀Alkylene or C₄-C₁₂Cycloalkylene radical

Y represents a polyurethane or polyurea block corresponding to the condensation of several diisocyanate molecules with one or more molecules of coupling agents of the diol or diamine type, corresponding to the formula:wherein, B¹Is selected from the groups given above for Y, U is-O-or-NH-, and B²Selected from:

●C₅-C₁₂cycloalkylene optionally containing alkyl substituents, such as 1-3 methyl or ethyl groups; or alkylene groups, such as diol groups:the cyclohexane dimethanol compound is a compound of cyclohexane dimethanol,

● may optionally contain C₁-C₃Phenylene with an alkyl substituent, and

● A group of the formula:

wherein T is a trivalent hydrocarbon-based radical possibly containing one or more heteroatoms such as oxygen, sulphur and nitrogen, R⁵Is a polyorganosiloxane chain or a linear or branched C₁-C₅₀An alkyl chain.

30. The composition of any of claims 1-19, wherein the polymer comprises at least one moiety having the formula:

wherein R is¹、R²、R³、m₁And m₂Having the meanings given above for formula (I),

-U represents O or NH,

A heteroatom, or represents phenylene, and

selecting 1-3C₁-C₃Alkyl-substituted phenyl.

31. The composition according to any one of claims 1 to 19, wherein the polymer used as gelling agent comprises at least one moiety having the formula:

wherein, X¹And X²Are identical or different and have the meaning given for X in claim 20, n, Y and T are as defined in claim 20, R¹¹-R¹⁸Is selected from R of claim 20¹-R⁴Same group, m₁And m₂Is a number in the range of 1 to 1000 and p is an integer in the range of 2 to 500.

32. The composition of any of claims 20-31, wherein the polymer used as a gelling agent further comprises a polymer comprising two hydrocarbon-based moieties capable of establishing hydrogen interactions, selected from the group consisting of ester, amide, sulfonamide, carbamate, thiocarbamate, urea and thiourea groups, and combinations thereof.

33. The composition of claim 31, wherein the copolymer is a block copolymer or a graft copolymer.

34. A composition according to any one of the preceding claims, wherein the polymer represents from 0.5% to 80% by weight of the total composition, preferably from 5 to 40%.

35. Composition according to any one of the preceding claims, in which the mass ratio gelling polymer/silicone oil is between 0.1% and 50%.

36. Composition according to any one of the preceding claims, in which the liquid fatty phase represents from 5% to 99% by weight of the total composition, preferably from 20% to 75%.

37. Composition according to any one of the preceding claims, characterized in that it constitutes a care and/or treatment and/or make-up composition for keratin materials.

38. Composition according to any one of the preceding claims, characterized in that it also contains at least one cosmetic makeup or skin active agent.

39. Composition according to any one of the preceding claims, characterized in that it contains at least one additive chosen from water, antioxidants, essential oils, preservatives, fragrances, liposoluble polymers, in particular hydrocarbon-based liposoluble polymers such as polyalkylene or polyvinyl laurate, aqueous phase gelling agents, liquid fatty phase gelling agents, waxes, gums, resins, surfactants such as triolein phosphate, additional cosmetic or dermatological active agents chosen from emollients, moisturizers, vitamins, liquid lanolin, essential fatty acids, liposoluble sunscreens or sunscreens soluble in polyols, and mixtures thereof.

40. Composition according to any one of the preceding claims, characterized in that it is in the form of a transparent anhydrous hydraulic gel, in particular in the form of a transparent anhydrous bar.

41. A structured solid cosmetic composition for the skin, lips and/or integuments, comprising at least one pigment in an amount sufficient to make up the skin, lips and/or integuments and a liquid continuous fatty phase comprising at least one silicone oil, structured with at least one polymer (homopolymer or copolymer) having a weight average molecular weight of 500-500000 and comprising at least one moiety comprising:

From 1 to 1000 organosiloxane units of the formula, and

Carbamates, thiocarbamates, ureas, thioureas, oxamido, guanidino,

And a biguanide group and combinations thereof, with the proviso that at least one of the groups is not an ester group, this polymer being solid at room temperature and soluble in the liquid fatty phase at a temperature of from 25 to 250 ℃, said liquid fatty phase being composed partially or totally of a volatile oil (or volatile oils) having a flash point greater than or equal to 40 ℃ and higher than the softening point of the gelling polymer, with the proviso that the composition comprises at least 10% by weight of a non-volatile oil and/or a pasty or viscous product, said composition being in solid form, and the pigment, the liquid fatty phase and the polymer forming a physiologically acceptable medium.

42. Composition according to claim 37, characterized in that it is self-supporting.

43. A structured lipstick composition comprising at least one pigment in an amount sufficient to make up the lips and a liquid continuous fatty phase comprising at least one silicone oil, structured with at least one polymer (homopolymer or copolymer) having a weight average molecular weight of 500-500000 and comprising at least one moiety comprising:

From 1 to 1000 organosiloxane units of the formula, and

Carbamates, thiocarbamates, ureas, thioureas, oxamido, guanidino,

And a biguanide group and combinations thereof, with the proviso that at least one of the groups is not an ester group, the polymer being solid at room temperature and soluble at a temperature of from 25 to 250 ℃ in the liquid fatty phase consisting partly or totally of a volatile oil (or volatile oils) having a flash point greater than or equal to 40 ℃ and higher than the softening point of the gelling polymer, with the proviso that the composition comprises at least 10% by weight of a non-volatile oil and/or a pasty or viscous product, the composition being in solid form and the pigment, the liquid fatty phase and the polymer forming a physiologically acceptable medium.

44. The composition of claim 40, wherein the polymer comprises at least one moiety corresponding to one of the following formulae: formula (I) according to claim 20, formula (II) according to claim 22, formulae (III) and (IV) according to claim 23, formula (VII) according to claim 27, formula (VIII) according to claim 29, formula (X) according to claim 30 and formula (XIII) according to claim 31.

45. Composition according to any one of claims 1 to 42, characterized in that it is in the form of a mascara cake, eyeliner, foundation, lipstick, blusher, deodorant preparation, makeup-removing preparation, body makeup preparation, eye shadow, face powder or make-up.

46. A cosmetic strip for the skin, the lips and/or a covering, in particular the lips, comprising at least one pigment in an amount sufficient to make up the skin, the lips and/or the covering and a liquid continuous fatty phase comprising at least one silicone oil, structured with at least one polymer (homopolymer or copolymer) having a weight average molecular weight of 500-500000 and comprising at least one moiety comprising:

From 1 to 1000 organosiloxane units of the formula, and

Carbamates, thiocarbamates, ureas, thioureas, oxamido, guanidino,

And a biguanide group and combinations thereof, with the proviso that at least one of the groups is not an ester group, the polymer being solid at room temperature and soluble at a temperature of from 25 to 250 ℃ in the liquid fatty phase consisting partially or totally of a volatile oil (or oils) having a flash point greater than or equal to 40 ℃ and higher than the softening point of the gelling polymer, with the proviso that the composition comprises at least 10% by weight of a non-volatile oil and/or a pasty or viscous product, the pigment, the liquid fatty phase and the polymer forming a physiologically acceptable medium.

47. A cosmetic care, makeup or treatment method for human keratin materials, comprising the application to the keratin materials of a cosmetic makeup composition according to any one of the preceding claims.

48. Use of a sufficient amount of at least one polymer (homopolymer or copolymer) in a cosmetic composition or for the manufacture of a physiologically acceptable composition comprising a liquid continuous fatty phase comprising at least one silicone oil, the liquid fatty phase being partially or totally composed of a volatile oil (or volatile oils) having a flash point greater than or equal to 40 ℃ and higher than the softening point of the gelling polymer, with the proviso that the composition comprises at least 10% by weight of a non-volatile oil and/or of a pasty or viscous product, so as to structure the composition in the form of a self-supporting solid having a hardness of 20-2000gf, preferably 20-900gf, more preferably 20-600gf, the weight-average molecular weight of the polymer being 500-500000, and containing at least one moiety comprising:

From 1 to 1000 organosiloxane units of the formula, and

Carbamates, thiocarbamates, ureas, thioureas, oxamido, guanidino,

49. Use according to the preceding claim, characterized in that said polymer comprises at least one moiety corresponding to one of the following formulae: formula (I) according to claim 20, formula (II) according to claim 22, formulae (III) and (IV) according to claim 23, formula (VII) according to claim 27, formula (VIII) according to claim 29, formula (X) according to claim 30 and formula (XIII) according to claim 31.

50. Use of a continuous liquid fatty phase comprising at least one silicone oil, substantially structured with a sufficient amount of at least one polymer (homopolymer or copolymer) having a weight average molecular weight of 500-500000, comprising at least one moiety comprising:

From 1 to 1000 organosiloxane units of the formula, and

Carbamates, thiocarbamates, ureas, thioureas, oxamido, guanidino,

And biguanide groups and combinations thereof, with the proviso that at least one of the groups is not an ester group, which polymer is solid at room temperature and soluble at a temperature of from 25 to 250 ℃ in the liquid fatty phase consisting partly or totally of a volatile oil (or volatile oils) having a flash point greater than or equal to 40 ℃ and higher than the softening point of the gelling polymer, with the proviso that the composition comprises at least 10% by weight of a non-volatile oil and/or a pasty or viscous product.

51. Use according to the preceding claim, characterized in that said polymer comprises at least one moiety corresponding to one of the following formulae: formula (I) according to claim 20, formula (II) according to claim 22, formulae (III) and (IV) according to claim 23, formula (VII) according to claim 27, formula (VIII) according to claim 29, formula (X) according to claim 30 and formula (XIII) according to claim 31.

52. Use of a sufficient amount of at least one polymer (homopolymer or copolymer) in a cosmetic composition or in the manufacture of a physiologically acceptable composition comprising a liquid continuous fatty phase comprising at least one silicone oil, consisting partially or totally of a volatile oil (or volatile oils) having a flash point greater than or equal to 40 ℃ and higher than the softening point of the gelling polymer, with the proviso that said composition comprises at least 10% by weight of a non-volatile oil and/or of a pasty or viscous product, in order to structure said composition in a self-supporting form, said polymer having a weight-average molecular weight of 500-500000 and comprising at least one fraction comprising:

From 1 to 1000 organosiloxane units of the formula, and

Carbamates, thiocarbamates, ureas, thioureas, oxamido, guanidino,

53. Use of a continuous liquid fatty phase containing at least one silicone oil, substantially structured with a sufficient amount of at least one polymer (homopolymer or copolymer) having a weight-average molecular weight of 500-500000, containing at least one moiety comprising:

From 1 to 1000 organosiloxane units of the formula, and

Carbamates, thiocarbamates, ureas, thioureas, oxamido, guanidino,

54. Use according to any one of claims 47 to 43, wherein the composition has a hardness of 20 to 2000gf, preferably 20 to 900gf, more preferably 20 to 600 gf.

55. Cosmetic process for limiting the migration of a cosmetic composition comprising a liquid fatty phase comprising at least one silicone oil, which comprises structuring said fatty phase with a sufficient amount of at least one polymer (homopolymer or copolymer) having a weight-average molecular weight of 500-500000 comprising at least one moiety comprising:

From 1 to 1000 organosiloxane units of the formula, and

Carbamates, thiocarbamates, ureas, thioureas, oxamido, guanidino,